The present invention relates to novel tetrazolinone derivatives, to processes for their preparation and to their use as herbicides.
It has already been known that certain kinds of tetrazole derivatives show herbicidal activity (Japanese Laid-open Patent Application Nos. 12275/1999 and 21280/1999). Moreover, it has further already been known, that certain kinds of heterocyclic derivatives also show herbicidal activity (U.S. Pat. Nos. 5,834,402 and 5,846,906).
The present invention provides novel tetrazolinones of the general formula (I) 
wherein
R1 represents halogen, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 alkylthio, C1-4 alkylsulfonyl, C1-4 alkylsulfonyloxy, C2-5 alkoxycarbonyl, C2-6 alkoxyalkyl, C2-6 alkylthioalkyl, nitro or cyano,
R2 represents a hydrogen atom, C1-6 alkyl, C3-6 cycloalkyl which may be optionally substituted with halogen or C1-3 alkyl, C1-4 haloalkyl, or phenyl which may be optionally substituted with halogen, C1-3 alkyl, C1-3 haloalkyl or nitro,
m represents 0, 1 or 2
n represents 0 or 1, and
Q represents one of the groups disclosed herein.
The present invention further provides methods of using the novel tetrazolinones as herbicides.
The present invention yet further provides a process for preparation of the novel tetrazolinones.
There have now been found novel tetrazolinone derivatives of the general formula (I) 
wherein
R1 represents halogen, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 alkylthio, C1-4 alkylsulfonyl, C1-4 alkylsulfonyloxy, C2-5 alkoxycarbonyl, C2-6 alkoxyalkyl, C2-6 alkylthioalkyl, nitro or cyano,
R2 represents a hydrogen atom, C1-6 alkyl, C3-6 cycloalkyl which may be optionally substituted with halogen or C1-3 alkyl, C1-4 haloalkyl, or phenyl which may be optionally substituted with halogen, C1-3 alkyl, C1-3 haloalkyl or nitro,
m represents 0, 1 or 2; while the two R1 substituents may be identical or different, in case m represents 2,
n represents 0 or 1, and
Q represents one of the following groups 
xe2x80x83in which
R3, R4, R5, R6, R7 and R8 each independently represent a hydrogen atom or C1-4 alkyl, or
R3 and R8 may form an ethylene chain together,
R9 represents C1-4 alkyl,
R10 represents C1-4 alkyl or C3-6 cycloalkyl which may be optionally substituted with methyl.
The compounds of the general formula (I), according to the invention, can be obtained by a process in which
a) compounds of the general formula (IIa) 
xe2x80x83wherein
R1, R2, m and n have the same definition as aforementioned, and
T1 represents one of the following groups 
xe2x80x83in which
R3, R4, R5, R6, R7, R8 and R9 have the same definition as mentioned above,
are reacted to a rearrangement in the presence of a base and a cyanide, or
b) in case that Q represents group (Q-2):
compounds of the general formula (IIb) 
wherein
R1, R2, m and n have the same definitions as mentioned above, and
T2 represents one of the following groups; 
xe2x80x83in which
R9 has the same definition as mentioned above,
are reacted to a rearrangement in the presence of a base, or
c) in case that Q represents group (Q-3):
compounds of the general formula (III) 
wherein
R1, R2, R10, m and n have the same definitions as mentioned above, and
R11 represents C1-4 alkyl, preferably methyl or ethyl,
are reacted with hydroxylamine, or
d) in case that Q represents group (Q-4):
compounds of the general formula (Ib) 
wherein
R1, R2, R10, m and n have the same definition as mentioned above,
are reacted to a ring-opening in the presence of a base.
The tetrazolinone derivatives of the general formula (I) provided by the present invention show a superior herbicidal activity compared with the compounds described in the aforementioned prior art literatures.
In the general formulae:
xe2x80x9cHalogenxe2x80x9d represents fluoro, chloro, bromo or iodo, and preferably represents fluoro, chloro or bromo.
xe2x80x9cAlkylxe2x80x9d may be straight or branched chain and there may be mentioned, for example, C1-6 alkyl specifically methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-, iso-, neo-, or tert-pentyl, n- or iso-hexyl.
As xe2x80x9ccycloalkylxe2x80x9d there can be mentioned, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. These cycloalkyls may be optionally substituted with halogen (for example, fluorine, chlorine or bromine), C1-3 alkyl (for example, methyl, ethyl, n- or iso-propyl) and in case a plurality of substituents exist, they may be identical or different.
As specific examples of such substituted cycloalkyls there can be mentioned 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-n-propylcyclopropyl, 1-methyl-2-fluoro-cyclopropyl, 2-methylcyclopropyl, 2-fluorocyclopropyl, 1-methyl-2,2-difluorocyclopropyl, 1-methyl-2,2-dichlorocyclopropyl, 2,2-difluorocyclopropyl, 2-methylcyclopentyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 2,5-dimethyl-cyclohexyl.
xe2x80x9cHaloalkylxe2x80x9d represents straight or branched chain alkyl, of which at least one hydrogen is substituted with halogen, and there may be mentioned, for example, C1-4 alkyl substituted with 1 to 6 fluorine atoms and/or chlorine atoms, and more specifically for example difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, di-chloromethyl, 2-chloro-1,1,2-trifluoroethyl, 3-fluoropropyl, 3-chloropropyl, 2,2,3,3,3-pentafluoropropyl or 1,2,2,3,3,3-hexafluoropropyl.
xe2x80x9cAlkoxyxe2x80x9d represents an xe2x80x94O-alkyl group, of which the alkyl part has the above-mentioned meaning. xe2x80x9cAlkoxyxe2x80x9d and can be, for example, C1-4 alkoxy, and more specifically for example methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec- or tert-butoxy.
xe2x80x9cAlkylthioxe2x80x9d represents an -S-alkyl group, of which the alkyl part has the above-mentioned meaning. xe2x80x9cAlkylthioxe2x80x9d can be, for example, C1-4 alkylthio, and more specifically for example methylthio, ethylthio, n- or iso-propylthio, n-, iso-, sec- or tert-butylthio.
xe2x80x9cAlkylsulfonylxe2x80x9d represents a xe2x80x94SO2-alkyl group, of which the alkyl part has the above-mentioned meaning. xe2x80x9cAlkylsulfonylxe2x80x9d can be, for example, C1-4 alkylsulfonyl, and more specifically for example methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso-, sec- or tert-butylsulfonyl.
xe2x80x9cAlkylsulfonyloxyxe2x80x9d represents a xe2x80x94Oxe2x80x94SO2-alkyl group, of which the alkyl part has the above-mentioned meaning. xe2x80x9cAlkylsulfonyloxyxe2x80x9d can be, for example, C1-4 alkylsulfonyloxy, and more specifically for example methylsulfonyloxy, ethylsulfonyloxy, n- or iso-propylsulfonyloxy, n-, iso-, sec- or tert-butylsulfonyloxy.
xe2x80x9cAlkoxycarbonylxe2x80x9d represents a xe2x80x94COxe2x80x94O-alkyl group, of which the alkyl part has the above-mentioned meaning. xe2x80x9cAlkoxycarbonylxe2x80x9d can be, for example, C2-5 alkoxycarbonyl, and more specifically for example methoxycarbonyl, ethoxycarbonyl, n- or iso-propoxycarbonyl, n-, iso-, sec- or tert-butoxycarbonyl.
xe2x80x9cAlkoxyalkylxe2x80x9d represents alkyl substituted with alkoxy and can be, for example, C2-6 alkoxyalkyl, and more specifically for example methoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 2-methoxy-1-methylethyl, methoxypropyl, methoxybutyl, methoxypentyl, ethoxymethyl, n- or iso-propoxymethyl, n-, iso-, sec- or tert-butoxymethyl.
xe2x80x9cAlkylthioalkylxe2x80x9d represents alkyl substituted with alkylthio and can be, for example, C2-6 alkylthioalkyl, and more specifically for example methylthiomethyl, methylthiomethyl, 1-methylthiopropyl, 2-methylthiopropyl, 1-methyl-2-methylthioethyl, methylthiobutyl, methylthiopentyl, ethylthiomethyl, n- or iso-propylthiomethyl, n-, iso-, sec- or tert-butylthiomethyl.
As a preferred group of compounds of the present invention there can be mentioned the compounds of the aforementioned general formula (I) wherein
R1 represents fluoro, chloro, bromo, methyl, ethyl, C1-2 haloalkyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, methoxycarbonyl, ethoxycarbonyl, C2-4 alkoxyalkyl, C2-4 alkylthioalkyl, nitro or cyano,
R2 represents a hydrogen atom, C1-4 alkyl, C3-5 cycloalkyl which may be optionally substituted with fluoro, chloro, bromo or C1-3 alkyl, C1-3 haloalkyl, or phenyl which may be optionally substituted with fluoro, chloro, bromo, methyl, ethyl, difluoromethyl or trifluoromethyl,
m represents 0, 1 or 2, while the two R1 substituents may be identical or different, in case m represents 2,
n represents 0 or 1, and
Q represents one of the following groups 
xe2x80x83wherein
R3, R4, R5, R6, R7 and R8 each independently represent a hydrogen atom, methyl or ethyl, and
R3 and R8 may form an ethylene chain together,
R9 represents C1-3 alkyl,
R10 represents tert-butyl or cyclopropyl which may be optionally substituted with methyl.
As a more preferable group of compounds there can be mentioned the compounds of the aforementioned general formula (I) wherein
R1 represents chloro, bromo, methyl, trifluoromethyl, methoxy, methylthio, methylsulfonyl, methylsulfonyloxy, methoxycarbonyl, methoxymethyl, methylthiomethyl or nitro,
R2 represents a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopropyl which may be optionally substituted with fluoro, chloro, methyl, ethyl or n-propyl, difluoromethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 2,2,3,3,3-pentafluoropropyl, or phenyl which may be optionally substituted with fluoro, chloro, methyl, difluoromethyl or trifluoromethyl,
m represents 0, 1 or 2, while two two R1 substituents may be identical or different, in case m represents 2,
n represents 0 or 1, and
Q represents one of the following groups 
xe2x80x83wherein
R9 represents methyl or ethyl,
R10 represents tert-butyl, cyclopropyl or 1-methylcyclopropyl.
The aforementioned preparation process a) is illustrated by the following reaction scheme for the case that for example, 3-oxo-1-cyclohexenyl 2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate is used as the starting material. 
The aforementioned preparation process b) is illustrated by the following reaction scheme for the case that, for example, 5-[2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoyloxy]-1-ethylpyrazole or 1-[2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoyl]-2-ethyl-2,3-dihydro-1H-3-pyrazolone are used as the starting material. 
The aforementioned preparation process c) is illustrated by the following reaction for the case that, for example, 3-cyclopropyl-1-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorophenyl}-2-ethoxymethylenepropane-1,3-dione and hydroxylamine is used as the starting material. 
The aforementioned preparation process d) is illustrated by the following reaction scheme for the case that, for example, 5-cyclopropyl-4-{3[(4cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorobenzoyl}isoxazole is used as the starting material. 
The compounds of the general formula (IIa), the starting material in the above-mentioned preparation process a) are novel compounds which were not described in the literature before the date of application of the present application and can be prepared according to the process described in the literature, for example, Japanese Laid-open Patent Application Nos. 222/1990, 173/1990 and 6425/1990 by reacting compounds of the general formula (IV) 
wherein
R1, R2, m and n have the same definition as mentioned above, and
M represents halogen,
with compounds of the general formula (V)
Q1xe2x80x94Hxe2x80x83xe2x80x83(V)
wherein
Q1 represents the following group 
or the group 
in which
R3, R4, R5, R6, R7, R8 and R9 have the same definition as mentioned above,
in an appropriate diluent, for example, dichloromethane, in the presence of an appropriate condensing agent, for example, triethylamine.
The compounds represented by the above-mentioned general formula (IV) are also novel compounds which were not described in the literature before the date of application of the present application and can be prepared, for example, by reacting compounds of the general formula (VI) 
wherein
R1, R2, m and n have the same definition as mentioned above,
with a halogenating agent, for example, phosphorous oxychloride, phosphorous oxybromide, phosphorous trichloride, phosphorous tribromide, phosgene, carbonyl bromide, oxalyl dichloride, thionyl chloride, thionyl bromide.
The compounds of the above-mentioned general formula (V) are commercially available or can be easily prepared according to the processes described in the literature, for example, Japanese Laid-open Patent Application Nos: 6425/1990, 265415/1998, 265441/1998, and 257974/1986.
The compounds of the above-mentioned general formula (VI) are also novel compounds which were not described in the literature before the date of application of the present application and can be prepared, for example, by hydrolyzing compounds of the general formula (VII) 
wherein
R1, R2, m and n have the same definition as mentioned above, and
R11 represents C1-4 alkyl, preferably methyl or ethyl,
in an appropriate diluent, for example, aqueous dioxane, in the presence of an appropriate base, for example, sodium hydroxide.
The compounds of the above-mentioned general formula (VII) are also novel compounds and the compounds, in case that n represents 0 in the general formula (VII), can be easily obtained, for example, by reacting compounds of the general formula (VIII) 
wherein
R1 and m have the same definition as mentioned above, and
R11 represents C1-4 alkyl, preferably methyl or ethyl,
with compounds of the general formula (IX)
R2xe2x80x94Mxe2x80x83xe2x80x83(IX)
wherein
R2 has the same definition as mentioned above, and
M represents halogen,
in an appropriate diluent, for example, N,N-dimethylformamide, in the presence of an appropriate condensing agent, for example, potassium carbonate.
The compounds of the above-mentioned general formula (VIII) are novel compounds which were not described in the literature before the date of application of the present application and can be easily prepared according to the process described in the literature, for example, Journal of Organic Chemistry, Vol. 45, 5130-5136 (1980), Journal of the American Chemical Society, Vol. 81, 3076-3079 (1959), Journal of the American Chemical Society, Vol. 72, 1888 (1950) by reacting- the isocyanic acid esters derived from compounds of the general formula (X) 
wherein
R1 and m have the same definition as mentioned above, and
R11 represents C1-4 alkyl, preferably methyl or ethyl,
with, for example, trimethylsilyl azide or sodium azide.
The compounds of the above-mentioned general formula (IX) are known and commercially available.
The compounds of the above-mentioned general formula (X) are also known and can be easily prepared according to the process described, for example, in Japanese Laid-open Patent Application No. 173/1990.
Further, the compounds of the above-mentioned general formula (VII), in case that n represents 1, can be easily obtained, for example, by reacting compounds of the general formula (XI) 
wherein
R2 has the same definition as mentioned above,
with compounds of the general formula (XII) 
wherein
R1 and m have the same definition as mentioned above,
R11 represents C1-4alkyl, preferably methyl or ethyl, and
M represents halogen,
in an appropriate diluent, for example, N,N-dimethylformamide, in the presence of an appropriate condensing agent, for example, potassium carbonate.
The compounds of the above-mentioned general formula (XI) are known compounds described, for example, in Japanese Laid-open Patent Application Nos. 97372/1995 and 134045/1996 and can be easily prepared according to.the process a described in the same references.
The compounds of the above-mentioned general formula (XII), a sub-group of which are novel compounds which were not described in the literature until now, can be easily prepared according to the process described, for example, in Japanese Laid-open Patent Application No. 173/1990.
Furthermore, the compounds of the general formula (IIa), starting material in the above-mentioned preparation process a), can be easily prepared from compounds of the general formula (VI) according to the process described, for example, in WO93/18031.
As typical examples of the compounds of the general formula (IIa), which are used as the starting material in the above-mentioned preparation process a), the following can be mentioned:
3-Oxo-1-cyclohexenyl 2-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate,
3-oxo-1-cyclohexenyl 2-[(4,5-dihydro-4-methyl-5oxo-1H-tetrazol-1-yl)methyl]benzoate,
3-oxo-1-cyclohexenyl 2-[(4-cyclohexyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-4-fluorobenzoate,
3-oxo-1-cyclohexenyl 4-chloro-2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl)benzoate,
3-oxo-1-cyclohexenyl 4-chloro-2-[(4,5-dihydro-4-ethyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,
3-oxo-1-cyclohexenyl 4-chloro-2-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,
3-oxo-1-cyclohexenyl 4-bromo-2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,
3-oxo-1-cyclohexenyl 2-((4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-trifluoromethylbenzoate,
3-oxo-1-cyclohexenyl 2-(4,5-dihydro-4-ethyl-5-oxo-1H-tetrazol-1-yl)-4-trifluoromethylbenzoate,
3-oxo-1-cyclohexenyl 2-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-4-nitrobenzoate,
3-oxo-1-cyclohexenyl 2-(4-difluoromethyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)-4-nitrobenzoate,
3-oxo-1-cyclohexenyl 2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-nitrobenzoate,
3-oxo-1-cyclohexenyl 2-[(4,5-dihydro-4-phenyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-nitrobenzoate,
3-oxo-1-cyclohexenyl 2-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-4-methylbenzoate,
3-oxo-1-cyclohexenyl 4-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate,
3-oxo-1-cyclohexenyl 2-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate,
3-oxo-1-cyclohexenyl 4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-fluorobenzoate,
3-oxo-1-cyclohexenyl 2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate,
3-oxo-1-cyclohexenyl 2,4-dichloro-3-[4,5-dihydro-4-(3-fluoropropyl)-5-oxo-1H-tetrazol-1-yl]benzoate,
3-oxo-1-cyclohexenyl 2,4-dichloro-3-[4-(n-butyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]benzoate,
3-oxo-1-cyclohexenyl 2,4-dichloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,
3-oxo-1-cyclohexenyl 2,4-dichloro-3-[(4-cyclopropyl4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,
3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[4-(4-bromophenyl)4,5-dihydro5-oxo-1H-tetrazol-1-yl]methyl}benzoate,
3-oxo-1-cyclohexenyl 2-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-I-yl)4-methylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 2-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-methylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 2-chloro-3-[(4cyclopropyl4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-4-methylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 2chloro-3-{[4,5-dihydro-4-(n-pentyl)-5-oxo-1H-tetrazol-1-yl]methyl}-4-methylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 2-chloro-3-{[4-(3-difluoromethylphenyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl}-4-metbylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 4-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-2-methylthiobenzoate,
3-oxo-1-cyclohexenyl 4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylthiobenzoate,
3-oxo-1-cyclohexenyl 2,4-di(methylthio)-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,
3-oxo-1-cyclohexenyl 4-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-2-methylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-methyl]-2-methylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 4-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-3-methoxybenzoate,
3-oxo-1-cyclohexenyl 2-chloro-4-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate,
3-oxo-1-cyclohexenyl 2-chloro-4-(4,5-dihydro-4-isopropyl-5-oxo-1H-tetrazol-1-yl)benzoate,
3-oxo-1-cyclohexenyl]2-chloro-4-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,
3-oxo-1-cyclohexenyl 2-bromo-4-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate,
3-oxo-1-cyclohexenyl 4-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methoxybenzoate,
3-oxo-1-cyclohexenyl 4-{[4-(2-chlorophenyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]methyl}-2-methoxybenzoate,
3-oxo-1-cyclohexenyl 4-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylsulfonyloxybenzoate,
3-oxo-1-cyclohexenyl 4-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)2-nitrobenzoate,
3-oxo-1-cyclohexenyl 4-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-nitrobenzoate,
5,5-dimethyl-3-oxo-1-cyclohexenyl 2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-trifluoromethylbenzoate,
5,5-dimethyl-3-oxo-1-cyclohexenyl 2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate,
4,4-dimethyl-3-oxo-1-cyclohexenyl 4-bromo-2-[(4,5-dihydrotmethyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,
4,4-dimethyl-3-oxo-1-cyclohexenyl 2,4-dichloro-3-[(4,5-dihydro4r-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,
4-{4-chloro-2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoyloxy}-bicyclo[3.2.1]-3-octen-2-one,
4-{2,4-dichloro-3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-benzoyloxybicyclo[3.2.1]-3-octen-2-one,
5-{2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4fluorobenzoyloxy}-1-methylpyrazole,
5-{4-bromo-2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoyloxy}-1-ethylpyrazole,
5-{4bromo-2-[(4,5-dihydro-4-ethyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoyloxy}-1-methylpyrazole,
5-{2-[(4,5-dihydro4-(n-propyl)-5-oxo-1H-tetrazol-1-yl)methyl]-4-trifluoromethylbenzoyloxy}-1-methylpyrazole,
5-[2-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)-4-methylbenzoyloxy]-1-ethylpyrazole,
5-[2-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)4trifluoromethylbenzoyloxy]-1-ethylpyrazole,
5-[2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoyloxy]-1-ethylpyrazole,
5-{2,4-dichloro-3-{[4-(tert-butyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]methyl}benzoyloxy}-1-ethylpyrazole,
5-[2-chloro-3(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-4methylsulfonylbenzoyloxy]-1-ethylpyrazole,
5-{2-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-methylsulfonylbenzoyloxy}-1-ethylpyrazole,
5-[4-chloro-3-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)-2-methylthiobenzoyloxy]-1-ethylpyrazole,
5-{4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylthiobenzoyloxy}-1-methylpyrazole,
5-{2,4-di(methylthio)-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-benzoyloxy}-1-ethylpyrazole,
5-[4-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-2-methylsulfonylbenzoyloxy]-1-ethylpyrazole,
5-{4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methyl-sulfonylbenzoyloxy}-1-ethylpyrazole,
5-[2-chloro-4-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoyloxy]-1-ethylpyrazole,
5-[2-chloro-4-(4-difluoromethyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)benzoyloxy]-1-methylpyrazole,
5-{2-chloro-4-[(4-cyclopropyl4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]benzoyloxy}-1-ethylpyrazole,
5-[2-bromo-4-(4,5-dihydro-4-ethyl-5-oxo-1H-tetrazol-1-yl)benzoyloxy]-1-methylpyrazole,
5-{4-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2-methoxybenzo-yloxy}-1-ethylpyrazole,
5-{4-[(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylsulfonyloxybenzoyloxy}-1-ethylpyrazole,
5-[4-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)-2-nitrobenzoyloxy]-1-methylpyrazole,
5-{4-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2-nitrobenzoyloxy}-1-ethylpyrazole.
The compounds of the general formula (IIb), the starting material in the above-mentioned preparation process b), are a sub-group of the compounds of the aforementioned general formula (IIa).
The compounds of the general formula (II), the starting material in the above-mentioned preparation process c), are novel compounds, which were not described in the literature before the date of application of the present application, and can be prepared according to the process described, for example, in Japanese Laid-open Patent Application No. 202008/1993 by reacting compounds of the general formula (XIII) 
wherein
R1, R2, R10, m and n have the same definition as mentioned above,
with compounds of the general formula (XIV)
HC(OR11)3xe2x80x83xe2x80x83(XIV)
wherein
R11 has the same definition as aforementioned,
in an appropriate diluent, for example, acetic anhydride.
The compounds of the above-mentioned general formula (XIII) are novel compounds, which were not described in the literature before the date of application of the present application, and can be prepared according to the process described, for example, in Japanese Laid-open Patent Application No. 202008/1993 by reacting compounds of the general formula (XV) 
wherein
R1, R2, R10, m, n and R11 have the same definition as aforementioned,
under an appropriate acidic condition in an appropriate diluent, for example, toluene in the presence of, for example, p-toluenesulfonic acid monohydrate.
The compounds of the above-mentioned general formula (XV) are novel compounds, which were not described in the literature before the date of application of the present application, and can be prepared according to the process described, for example, in Japanese Laid-open Patent Application No. 202008/1993 by reacting compounds of the above-mentioned general formula (IV) with, for example, a complex obtained by treating compounds of the general formula (XVI) 
wherein
R10 has the same definition as aforementioned,
R12 represents C1-4 alkyl,
with magnesium and carbon tetrachloride.
The compounds of the above-mentioned general formula (XVI) are commercially available or can be prepared according to the process described, for example, in Journal of Organic Chemistry, Vol. 43, 2087 (1978).
The compounds of the above-mentioned general formula (XVI) are already known.
As typical examples of the compounds of the general formula (III), which are used as the starting material in the above-mentioned preparation process c), the following can be mentioned:
3-Cyclopropyl-1-{2-[(4,5-dihydro-4-ethyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-fluorophenyl)}-2-ethoxymethylenepropan-1,3-dione,
3-cyclopropyl-1-{4-chloro-2-[(4,5-dihydro4-ethyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-phenyl}-2-etdoxymethylenepropan-1,3-dione,
3-cyclopropyl-1-{2-[(4-cyclopropyl4,5-dihydro -5-oxo-1H-tetrazol-1-yl)methyl]-4-trifluoromethylphenyl}-2-ethoxymethylenepropan-1,3-dione,
3-cyclopropyl-1-[2-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-4-trifluoromethylphenyl]-2-ethoxymethylenepropan-1,3-dione,
3-cyclopropyl-1-{4-chloro-3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2-fluorophenyl}-2-ethoxymethylenepropan-1,3-dione,
3-cyclopropyl-1-[2,4-dichloro-3-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)phenyl]-2-ethoxymethylenepropan-1,3-dione,
3-cyclopropyl-1-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorophenyl}-2-ethoxymethylenepropan-1,3-dione,
3-cyclopropyl-1-{2-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-methylsulfonylphenyl}-2-ethoxymethylenepropan-1,3-dione,
3-cyclopropyl-1-[4-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-2-methylthiophenyl]-2-ethoxymethylenepropan-1,3-dione,
3-cyclopropyl-1-{4-chloro-3-[(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylsulfonylphenyl}-2-ethoxymethylenepropan-1,3-dione,
3-cyclopropyl-1-[2-chloro4-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)phenyl]-2-ethoxymethylenepropan-1,3-dione,
3-(tert-butyl)-1-{2-chloro-3-[(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-methylsulfonylphenyl}-2-ethoxymethylenepropan-1,3-dione.
The compounds of the general formula (Ib), the starting material in the above-mentioned preparation process d), are a sub-group of the compounds of the general formula (I) of the present invention and can be easily prepared according to the above-mentioned preparation process c).
As typical examples of the compounds of the general formula (Ib), which are used as the starting material in the above-mentioned preparation process (d), there can be mentioned the following which are included in the general formula (I):
4-{4-Chloro-2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoyl}-5-cyclopropylisoxazole,
5-cyclopropyl-4-[2-(4,5-dihydro-4-methyl-S -oxo-1H-tetrazol-1-yl)-4-nitrobenzoyl]-isoxazole,
4-{2-[(4-cyclohexyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-4-nitrobenzoyl}-5-cyclopropylisoxazole,
4-[2,4-dichloro-3-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)benzoyl]-5-cyclopropylisoxazole,
4-{2,4-dichloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoyl}-5-cyclopropylisoxazole,
4-{2-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-methylsulfonylbenzoyl}-5-cyclopropylisoxazole,
4-{4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylthiobenzoyl}-5-cyclopropylisoxazole,
4-[2-chloro4-(4,5-dihydro4methyl-5-oxo-1H-tetrazol-1-yl)benzoyl]-5-cyclopropylisoxazole.
The general formulae (IIa), (IIb), (III), (IV), (VI), (VII), (VIII), (XIII) and (XV) of the novel starting materials and intermediates in the preparation processes of the compounds of the above-mentioned general formula (I) of the present invention can be represented collectively by the following general formula (XVII) 
wherein
W represents T1, M, hydroxy, or one of the following groups OR11, 
xe2x80x83in which
R1, R2, R10, R11, m, n, T1 and M have the same definition as mentioned above.
The reaction of the above-mentioned preparation process a) can be conducted in an appropriate diluent. As examples of such diluents used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, toluene, dichloromethane, chloroform or 1,2-dichloroethane; ethers, for example, ethyl ether, dimetboxyethane (DME) or tetrahydrofuran (THF); ketones, for example, methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile; esters, for example, ethyl acetate; acid amides, for example, dimethylformamide (DMF).
The preparation process a) can be conducted in the presence of a cyanide and a base. As a cyanide employable in that case there can be mentioned, for example, sodium cyanide, potassium cyanide, acetone cyanohydrin or hydrogen cyanide. As a base there can be mentioned, for example, as inorganic bases, hydroxides, carbonates etc. of alkali metals and alkaline earth metals, for example, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide; and as organic bases, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2,2,2]octane (DABCO) or 1,8-diazabicyclo[5,4,0]undec-77-ene (DBU).
The above-mentioned preparation process a) can be conducted also by adding a phase-transfer catalyst to the reaction mixture. As examples of the phase-transfer catalyst employable in that case there can be mentioned crown ethers, for example, dibenzo-18-crown-6, 18-crown-6, 15-crown-5.
The preparation process a) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about xe2x88x9210 to about 80xc2x0 C., preferably about 5 to about 40xc2x0 C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.
In conducting the preparation process a) the aimed compounds of the above-mentioned general formula (I), in case that Q represents groups (Q-1) or (Q-2), can be obtained, for example, by reacting 1 mole of a compound of the general formula (II) with 1 to 4 moles of triethylamine in a diluent, for example, acetonitrile, in the presence of 0.01 to 0.5 moles of acetonecyanohydrin.
The reaction of the above-mentioned preparation process b) can be conducted in an appropriate diluent. As examples of such diluents used in that case there can be mentioned ethers, for example, dioxane, tetrahydrofuran (THF); alcohols, for example, tert-amyl alcohol or tert-butyl alcohol.
The preparation process b) can be conducted in the presence of a base. As a base employable in that case there can be mentioned as inorganic bases, carbonates of alkali metals, for example, sodium carbonate or potassium carbonate; and as organic bases, tertiary amines, for example, triethylamine, pyridine or 4-dimethylaminopyridine (DMAP).
The preparation process b) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about 5 to about 200xc2x0 C., preferably about 25 to about 130xc2x0 C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.
In conducting the preparation process b) the aimed compounds of the aforementioned general formula (I), in case that Q represents group (Q-2), can be obtained by reacting 1 mole of a compound of the general formula (II) with 0.5 to 2 moles of potassium carbonate in a diluent, for example, dioxane.
The reaction of the above-mentioned preparation process c) can be conducted in an appropriate diluent. As examples of such diluents used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, toluene, dichloromethane, chloroform or 1,2-dichloroethane; ethers, for example, tetrahydrofuran (THF); nitrites, for example, acetonitrile; alcohols, for example, methanol, ethanol or isopropanol.
The preparation process c) can be conducted in the presence of a base. As a base employable in that case there can be mentioned, as inorganic bases, acetates, carbonates, bicarbontes etc. of alkali metals and alkaline earth metals, for example, sodium acetate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate or potassium carbonate; and as organic bases, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, pyridine or 4-dimethylaminopyridine (DMAP).
The preparation process c) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about xe2x88x9210 to about 100xc2x0 C., preferably about 0 to about 50 xc2x0 C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.
In conducting the preparation process c) the aimed compounds of the general formula (I), in case that Q represents group (Q-3) can be obtained, for example, by reacting 1 mole of a compound of the general formula (III) with 1 to 1.5 moles of hydroxylamine hydrochloride in a diluent, for example, ethanol in the presence of 1 to 1.5 moles of sodium acetate.
The reaction of the above-mentioned preparation process d) can be conducted in an appropriate diluent. As examples of such diluents used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride or 1,2-dichloroethane; ethers, for example, ethyl ether, dioxane, dimethoxyethane (DME) or tetrahydrofuran (THF); nitrites, for example, acetonitrile; alcohols, for example, methanol, ethanol or isopropanol; esters, for example, ethyl acetate; acid amides, for example, dimethylformamide (DMF).
The preparation process d) can be conducted in the presence of a base. As a base employable in that case there can be mentioned, as inorganic bases, hydroxides, carbonates etc. of alkali metals and alkaline earth metals for example, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide; and as organic bases, alcoholates, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA) or 4-dimethylaminopyridine (DMAP).
The preparation process d) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about xe2x88x9210 to about 100xc2x0 C., preferably about 0 to about 50xc2x0 C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.
In conducting the preparation process d) the aimed compounds of the aforementioned general formula (I), in case Q represents group (Q4), can be obtained, for example, by opening the ring of 1 mole of a compound of the general formula (Ib) in a diluent, for example, dichloromethane in the presence of 1 to 3 moles of triethylamine.
In conducting the preparation process a) the compounds of the general formula (I) can be obtained by starting from a compound of the general formula (VI) and continuously reacting without isolating the compounds of the general formula (IV) and the compounds of the general formula (II). And in the preparation process b) the compounds of the general formula (I) can be also obtained by starting from a compound of the general formula (VI) and continuously reacting without isolating the compounds of the general formula (IV) and the compounds of the general formula (II). In conducting the preparation process c) the compounds of the general formula (I) can be obtained by starting from a compounds of the general formula (IV) and continuously reacting without isolating the compounds of the general formula (XV) to obtain the compound of the general formula (XIII), and then by starting from a compounds of the general formula (XIII) and continuously reacting without isolating the compounds of the general formula (III).
The active compounds of the aforementioned general formula (I), according to the present invention, show, as shown in the biological test examples to be described later, excellent herbicidal activities against various weeds and can be used as herbicides. In the present specification weeds mean, in the broadest sense, all plants which grow in locations where they are undesired.
The compounds of the present invention act as total or selective herbicides depending upon the applied concentration. The active compounds, according to the present invention, can be used, for example, between the following weeds and cultures.
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea, Polygonum, Ambrosia, Cirsiumn, Sonchus, Solanum, Rorippa, Lamiumn, Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga, Rotala, Linderia etc.
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita etc.
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Cynodon etc.
Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium etc.
The use of the compounds, according to the present invention, is not restricted to the above-mentioned plants, but may be applied to other plants in the same manner. The active compounds, according to the present invention, can, depending upon the applied concentration, non-selectively control weeds and may be used, for example, on industrial terrain, rail tracks, paths, places with or without tree plantings. Moreover, the active compounds, according to the present invention, can be used for controlling weeds in perennial cultures and applied in, for example, afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings, hopfields and can be applied also for the selective controlling of weeds in annual cultures.
According to the invention all plants and plant parts can be treated. The term plants includes all plants and plant populations, such as desired or undesired wild plants and cultivated plants (including naturally occurring cultivated varieties). Cultivated plants can be plant varieties that were obtained by conventional breeding and optimizing processes or by biotechnological and genetic engineering methods or a combination of such processes and methods, including transgenic plants and including plant varieties that cannot or can be protected by plant patents or plant variety rights. Plant parts are all parts and organs of plants occurring above or below the surface of the soil, e.g. shoots, leaves, needles, stalks and stems, trunks, flowers, fruits and seeds as well as roots, tubers, bulbs and rhizomes. The term plants parts also includes harvested crops and propagation material, e.g. cuttings, tubers, bulbs, rhizomes, shoots and seeds.
According to the invention the plants and plants parts are treated using the usual methods by applying the active ingredients or compositions containing them directly to the plants or plant parts or to their surroundings (including the soil) or storeroom, e.g. by dipping, spraying, dusting, fogging, spreading and in the case of propagation material also by coating using one or multiple layers.
The active compounds, according to the present invention, can be made into customary formulations. As such formulations there can be mentioned, for example, solutions, wettable powders, emulsions, suspensions, powders, water-dispersible granules, tablets, granules, suspension-emulsion concentrates, microcapsules in polymeric substances or jumbo formulations.
These formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid or solid diluents or carriers, and optionally with surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents.
As liquid diluents or carriers there can be mentioned, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride), aliphatic hydrocarbons [for example, cyclohexane or paraffins (for example, mineral oil fractions)], alcohols (for example, butanol, glycol) and their ethers, esters etc., ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), strongly polar solvents (for example, dimethylformamide, dimethyl sulphoxide) and water. In case of using water as an extender, for example, organic solvents can be used as auxiliary solvents.
As solid diluents or carriers there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth) or ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates). As solid carriers for granules there can be mentioned, for example, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite), synthetic granules of inorganic and organic meals or particles of organic material (for example, sawdust, coconut shells, maize cobs and tobacco stalks).
As emulsifiers and/or foam-forming agents there can be mentioned, for example, nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters or polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates)] and albumin hydrolysis products.
As dispersants there are included, for example, ligninsulphite waste liquor and methyl cellulose.
Tackifiers may also be used in formulations (powders, granules, emulsions). As said tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate).
Colorants may also be used. As said colorants there can be mentioned inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue) and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further trace nutrients such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum, zinc.
Said, formulations can contain in a range of generally 0.1 to 95% by weight, preferably 0.5 to 90% by weight of the active compounds of the general formula (I).
The active compounds of the general formula (I), according to the present invention, can be used as such or in form of their formulation for controlling weeds. They can be used also as a mixed agent with other known herbicides. Such a mixed agent can be previously prepared as a form of final formulation or can be prepared by tank-mixing on occasion of the application. As a possible mixing partner in such combinations there can be mentioned, for example, known herbicides such as sulfonylurea type herbicides for paddy field use.
Furthermore, the active compounds of the general formula (I), according to the present invention, can be mixed also with a safener and their application as a selective herbicide may be broadened by such a mixing. As an example of such safener 1-(xcex1,xcex1-dimethylbenzyl)-3-p-tolylurea can be mentioned.
Surprisingly, some of the combinations of the compounds according to the present invention with other mixing partners show synergistic effects.
In case of using the active compounds of the general formula (I), according to the present invention, they can be directly used as such or in form of formulations such as ready-to-use solutions, emulsions, tablets, suspensions, powders, pastes, granules or used in the use forms prepared by further dilution. The active compounds, according to the present invention, can be applied by means of, for example, watering, spraying, atomizing or granule application.
The active compounds of the general formula (I), according to the present invention, can be used at any stages before and after germination of plants. They may also be applied to the soil before sowing.
The application rates of the active compounds, according to the present invention, may be varied in a substantial range and are fundamentally different according to the nature of the desired effect. In case of herbicidal use, as the application rate there can be mentioned, for example, ranges of about 0.01 to about 4 kg, preferably about 0.05 to about 3 kg of the active compounds per hectare.